Novel process for altering the organoleptic properties of tobacco using one or more alpha-pyrones and process

ABSTRACT

Described is a process comprising adding to tobacco an amount sufficient to alter the flavor or aroma of the tobacco, one or more alpha-pyrone compounds having the generic structure:   WHEREIN R1 is methyl or hydrogen, and R2 is C3-C5 alkyl; processes for producing such tobacco products; and flavor formulations for use in conjunction with tobacco products containing one or more of such alpha-pyrones.

United States Patent [191 Vinals et al.

Abrahamsville, Pa.; Alan Owen Pittet, Atlantic Highlands, NJ.

[73] Assignee: International Flavors & Fragrances Inc., New York, NY.

[ Notice: The portion of the term of this patent subsequent to Jan. 21, 1992, has been disclaimed.

[22] Filed: Sept. 4, 1974 [21] Appl. No.: 503,110

Related US. Application Data [62] Division of Ser. No. 471,785, May 20, 1974, Pat. No.

[52] US. Cl. 131/144; 131/17 R [51] Int. Cl A24b 15/04 [58] Field of Search 131/2, 1'5, 17, 9, 140-144 [56] References Cited UNITED STATES PATENTS 3,380,457 4/1968 Schumacher et a1. 131/17 R FOREIGN PATENTS OR APPLICATIONS 748,645 5/1956 United Kingdom l3l/144 X ]*June 24, 1975 Primary Examiner-Melvin D. Rein Attorney, Agent, or Firm-Arthur L. Liberman, Esq.; Harold Haidt, Esq.

[57] ABSTRACT Described is a process comprising adding to tobacco an amount sufficient to alter the flavor or aroma of the tobacco, one or more alpha-pyrone compounds having the generic structure:

wherein R is methyl or hydrogen, and R is C -C alkyl; processes for producing such tobacco products; and flavor formulations for use in conjunction with tobacco products containing one or more of such alphapyrones 6 Claims, No Drawings NOVEL PROCESS FOR ALTERING THE ORGANOLEPTIC PROPERTIES OF TOBACCO USING ONE OR MORE ALPHA-PYRONES AND wherein one or more of R R and R are hydrogen or alkyl and wherein the dashed line represents a single bond or a double bond. Schumacher et al. states that PROCESS an aroma and flavor which is reminiscent of coconut 5 may be imparted by the use of 3-isopropyl-delta- This application is a division of applicants copending valerolactone as a tobacco additive; or by the use of 5- Patent Application Ser. No. 471,785 filed on May 20, hydroxy-3-isopropyl-2-pentenoic acid delta lactone, as

1974, now U.S. Pat. No. 3,861,403. a tobacco additive; or a spicy note may be imparted by BACKGROUND OF THE INVENTION $3555 iffifi fiiiifiiifii ll li 1 de'ta picy app e not may This invention relates to novel tobacco products, be imparted by the use of beta-methyl-delta valerolacnovel tobacco flavoring compositions, and processes tone as a tobacco additive.

for producing same, and has for an object the provision Various alpha pyrones have been described as being of a composition and process for improving the flavor l5 useful in altering the organoleptic characteristics of flaand aroma of tobacco and tobacco smoke.

It is well known in the tobacco art that the flavor and aroma of the tobacco product and the smoke from the tobacco are very important considerations insofar as the ultimate consumer is concerned. Considerable efvors for foodstuffs as well as fragrances for use in conjunction with perfumed articles.

Arctander, Perfume and Flavor Chemicals (Aroma Chemicals) 1969 contains the following teachings:

forts have been and are being exerted by the manufac- 2 2:: igzg flavor and perfume use of 5 ethyl turers of tobacco products to provide a product that will be acceptable to the consumer, particularly as reii ifi ziz yigij and perfume use of gards flavor l? 9 s i f been the iii. At No. 2781, the perfume use of alpha pyrone. common prac we m e to acco m us ry 0 Prepare Taylor et al. British Pat. No. 748,645 discloses at page blends of domestic and oriental tobaccos in order to provide smoking tobacco which has a pleasing flavor and aroma before and during smoking. However, such a procedure is costly and may at times become prohibitive in the event that certain types of tobacco may be in short supply. Accordingly, there has been considerable work relating to substances which can be used to impart flavors to various tobacco blends. These substances are used to supplementnatural materials some of which, as stated above, may be in short supply, and to provide more uniform properties to the finished product.

Sweet, aromatic, warm, spicy, maple-like, fruity, coumarin-like, vanillin-like, lactone, lovage-like, celery-like and nut-like notes are paticularly desirable for many uses concerning theflavoring of tobacco products; both prior to and on smoking.

Schumacher et al., U.S. Pat. No. 3,380,457 issued on Apr. 30, 1958 described an improved tobacco product Methods for the preparation of the alpha-pyrones found to be useful in our invention are disclosed as fol- 4O lows:

i. Lohaus et al., Chemische Berichte, 100,v 658 ii. Wiley et al., J.Org.Chem., 22. 1257-9, (1957);

iii. Belgian Pat. NO. 643,891, Aug. 17, 1964;

containing a lactone Compound having the generic iv. Nobuhara,Agr.Biol.Chem. 1969,33(9), 1264-9; structure: v. Pettit et al., J. Org.Chem., 1970, 35(5),

1398-1404; vi. Lamberti et al., Recueil, 86 (1967) 504510:

The .6-alkyl-alpha-pyrones of our invention, which are unsubstituted at the 4position of the pyrone ring may also be prepared according to the process of copending U.S. Application for Letters Patent No. 471,756 filed on May 20, 1974 the reactions of which are as follows:

Hot column 500 Packed with Cir-packing yield wherein R is alkyl.

THE INVENTION It has now been discovered that tobacco flavoring compositions and tobacco products having sweet, aromatic, warm, spicy, maple-like, fruity, coumarin-like,

vanillin-like, lactonic, lovage-like, celery-like and/or nut-like flavors and aromas prior to and on smoking may be provided by adding to tobacco flavors and/or to tobaccos themselves one or more alpha pyrones having the generic structure:

wherein R is hydrogen or methyl and R is C -,-C alkyl. Thus, the groups exemplified by R are as follows:

n-P py i-propyl n-butyl i-butyl t-butyl l-pentyl Z-pentyl Organoleptic Properties Organoleptic Prior to Properties Compound Smoking On Smoking 6-n-propyl- Creamy, sweet, Sweet, aromatic alpha-pyrone coumarin, herbal lactone, coumarin,

note vanillin taste and aroma 6-n-butyl- Sweet, slightly Sweet, aromatic, alpha-pyrone coumarin, and coconut, coumarin- 5 5 floral aroma vanillin, and

lactone aroma and taste -i-butyl- Sweet and Sweet, aromatic, alpha-pyrone coconut-like and creamy-vanillin-like taste and aroma 6-n-pentyl- Green, floral Fruity, coumarinalpha-pyroneand coconutlike taste and like aroma aroma 4-methyl-6-i- Sweet, rum-like Sweet, aromatic, propyl-alphalovage, tagette warm spicy and pyrone with tonka underlovage-like taste tone and aroma 4-methyl-6-n- Sweet, coumarin- Spicy, celery-like, butyl-alphalike, foenugreek fatty, creamy, pyrone like, celerycereal and nut-like like aroma taste and aroma 4-methyl-6-i- Sweet, fruity, Sweet, aromatic, butyl-alphajasmine-like, warm, spicy, pryone appley aroma somewhat maple- It has been found that the tobacco additives of our invention when incorporated into tobacco products impart a flavor and aroma both before and during smoking which many smokers consider to be desirable in smoking products. However, it is pointed out that the methods for defining or characterizing the quality of a flavor or aroma in the tobacco art are almost purely subjective and different smokers may define the same flavor quite differently. Also, as indicated in the above table, the compounds included within the broad scope of this invention may impart different flavors or aromas depending upon the alkyl substituent s therein. Thus, the compounds comprehended by this invention, by subjective tests, impart characteristic flavors which are desirable in tobacco products and the smoke therefrom even though the exact character thereof cannot be described on the basis of known standards.

In accordance with this invention, one or more of the alpha-pyrones of our invention, or mixtures thereof, is added to tobacco or applied to a smoking article or its component parts in amounts'of about -5000 parts per million (ppm) based on dry weight of the tobacco product. Preferably, the amount of additive is between about 200 and 500 ppm by weight in order to provide a tobacco product having a desired flavor and aroma. However, the amount used will depend upon the amound of flavor and aroma desired and the particular compound or mixture thereof that is used. The additive may be incorporated at any step in the treatment of the tobacco but is preferably added after aging, curing and shredding and before the tobacco is formed into cigarettes. Likewise, it will be apparent that only a portion of thetobacco need be treated and the thus treated tobacco may be blended with other tobaccos before the cigarettes or other smoking articles are formed. In such case the tobacco treated may have the additive in excess of the amounts above indicated so that when blended with other tobaccos the final product will have the percentage within the indicated range.

In accordance with one specific embodiment of this invention, an aged, flue-cured and shredded tobacco is sprayed with a 1% ethyl alcohol solution of 6-n-pentylalpha-pyrone in an amount to provide a tobacco containing 200 ppm. by weight of the additive on a dry basis. Thereafter, the alcohol is removed by evaporation and the tobacco is manufactured into cigarettes by the usual techniques. It has been found that the cigarette when prepared as indicated has a desired and pleasing flavor, an aroma which to some people is described as "fruity-coumarine-like" and is detectable and pleasing in the main and side smoke streams when the cigarette is smoked.

The additives falling within the scope of this invention may be applied to the tobacco by spraying, dipping or otherwise, utilizing suitable suspensions or solutions of the additive. Thus water or volatile organic solvents, such as alcohol, ether, acetone, volatile hydrocarbons and the like, may be used as the carrying medium for' the additive while it is being applied to the tobacco.

Also, other flavor-and aroma-producing additives, such a. Esters, for example:

Ethyl butyrate; Ethyl acetate; Ethyl valerate; Amyl acetate; Phenyl ethyl isovalerate; and Methyl heptynyl carbonate b. Aldehydes, for example:

3-phenyl-2-pentenal; 3-phenyl-3-pentenal; phenyl acetaldehyde; Cinnamaldehyde; and Beta-ethylcinnamaldehyde c. Ketones, for example:

Benzylidene acetone; Acetophenone; Maltol; and

Ethyl maltol d. Acetals, for example: 7

3-phenyl-4-pentenal dimethyl acetal; and 3-phenyl- 4-pentenal diethyl acetal (described in copending application for U.S. Letters Patent No. 276,922 filed on Aug. 1, 1972) e. Natural oils and extracts, for example:

Vanilla; Coffee extract; Origanum Oil; Cocoa Extract; Oil of Cloves; Nutmeg Oil; Celery seed oil; Bergamot oil; and Ylang-ylang oil f. Lactones, for example:

Delta-decalactone; Delta-undecalactone; Deltadodecalactone; Gamma-undecalactone; and Coumarin g. Ethers, for example:

Dibenzyl ether; Vanillin; and Eugenol h. Pyrazines, for example:

2-Acetyl pyrazine; 2-Acetyl-6-methyl pyrazine;

2Ethyl pyrazine; 2,3-Dimethyl pyrazine; 2,5- Dimethyl pyrazine; and 2Ethyl-5-methyl pyrazine i. Pyrroles, for example:

N-cyclopropyl pyrrole; and N-cyclooctyl pyrrole as well as those additives disclosed in U.S. Pat. Nos. 2,766,145, 2,905,575, 2,905,576, 2,978,365, 3,041,211, 2,766,149, I 2,766,150, 3,589,372, 3,288,146, 3,402,051 and 3,380,457 as well as Australian Pat. Nos. 444,545, 444,507 and 444,389 may be incorporated into the tobacco with the additives of this invention.

While this invention is principally useful in the manufacture of cigarette tobacco, it is also suitable for use in connection with the manufacture of pipe tobacco, cigars or other tobacco products. Furthermore, the compounds may be added to' certain tobacco substitutes of natural or synthetic origin.

Also, the invention has been particularly described with reference to the addition of the compounds directly to'tobacco. However, it will be apparent that the compound may be applied to thepaper of the cigarette or to the wrapper of a cigar. Also, it may be incorporated into the filter tip, the packaging material on' the seam paste employed for gluing the cigarette paper. Thus, a tobacco product is provided which includes the specified additives and tobacco although in every instance the compound need not be admixed with the tobacco as above specifically described.

The following examples are given to illustrate the embodiments of the invention as it is presently preferred to practice it. It will be understood that these examples are illustrative and the invention is not to be considered as restricted thereto except as indicated in the appended claims.

EXAMPLE I TOBACCO USE OF 6-ALKYL-ALPHA-PYRONE The following tobacco flavor formulation A is prepared:

A tobacco formulation B is prepared as follows:

Ingredients Bright Tobacco 40. Burley Tobacco 24 Maryland Tobacco 1 Turkish Tobacco l 1. Stem (Flue-cured) Tobacco l4. Glycerine 2 Water 5 The flavor formulation A is added to a portion of the smoking tobacco formulation B at the rate of 0.1% by weight of the tobacco. The flavored and non-flavored tobacco formulations are then formulated into cigarettes by the usual manufacturing procedures:

i. At the rate of 200 ppm to one-seventh of the cigarettes in each group is added 4-methyl-6-n-pentylalpha-pyrone. The use of the 4-methyl6-n-pentylalpha-pyrone in the cigarettes causes the cigarettes prior to smoking to have a celery, lovage, tagette aroma. In smoke flavor, these notes are not found, however, on smoking the cigarettes containing the 4 methyl-6-n-petnyl-alpha-pyrone are found to be more richer, sweeter and spicier and to have maple, creamy and vanilla notes whether or not the other flavor ingredients of formulation A are present.

ii. At the rate of 200 ppm to one-seventh of the cigarettes in each group is added 4-methyl-6-n-butylalpha-pyrone. The use of the 4-methyl-6-n-butylalpha-pyrone at this level causes the tobacco prior to smoking to have a sweet coumarin-like, foenugreek-like and celery-like aroma. On smoking, the foenugreek-line aroma is not perceived in the smoke flavor; However, the cigarettes are found to have a spicy, celery-like, fatty, creamy, cereal and nut-like aroma'and taste and to be sweeter and spicier than the same formulation without the 4- methyl-6-n-butyl-alpha-pyrone whether or not the other. flavor ingredients of formulation A are present therein.

iii. At the rate of 500 ppm to one-seventh of the cigarettes in each group is added 6-n-propyl-alphapyrone. The use of the 6-n-propyl-alpha-pyrone in the cigarettes causes the cigarettes prior to smoking to have a creamy, sweet coumarin-like, herbal aroma. in smoke flavor, the herbal note is not found, however, on smoking, the cigarettes containing the 6-n-propyl-alpha-pyrone are found to have a sweet, aromatic, lactone, coumarin, vanillin-like taste and aroma, whether or not the other flavor ingredients of formulation A are present. iv. At the rate of 200 ppm to one-seventh ofthe cigarettes in each group is added 4-methyl-6-isopropylalpha-pyrone. The use of the 4-methyl-6-isopropylalpha-pyrone at this level causes the tobacco prior to smoking to have a sweet rum-like, lovage, tagette aroma with a tonka undertone. On smoking, rum-like aroma is not perceived in the smoke flavor. However, the cigarettes are found to have sweet, aromatic, warm, spicy, lovage-like taste and aroma notes not existing in the same formulation without the 4-methyl-6-isopropyl-alpha-pyrone whether or not the other flavor ingredients of formulation A are present therein. At the rate of 500 ppm to one-seventh of the cigarettes in each group is added 6-n-butyl-alphapyrone. The use of the 6-n-butyLalpha-pyrone at this level causes the tobacco prior to smoking to have a sweet and floral aroma with a slight coumarin-like character. On smoking, the floral note is not perceived in the smoke flavor. However, the cigarettes on smoking are found to have a sweet, aromatic, coconut, coumarin-vanillin, lactone taste and aroma, whether or not the other flavor ingredients of. formulation A are present. vi. At the rate of 200 ppm to one-seventh of the ciga- I rettes in each group is added 6-n-pentyl-alphapyrone. Theuse of 6-n-pentyl-alpha-pyrone at this level in. the cigarettes causes the cigarettes prior to smoking to have a green, floral and coconut aroma, significantly more intense than cigarettes containing' delta-dodecalactone. In smoke flavor, these notes are not found, however, on smoking, the cigarettescontaining the 6-n-pentyl-alpha-pyrone are found to. have a marked fruity, coumarin-like taste and aroma whether or not the other ingredients in formulation A are present. One-seventh of the cigarettes remains totally without added vflavorants. One-seventh of the cigarettes contains only formulation A added thereto; but no 6-alky1- alpha-pyrone. V

In general, onsmoking, the cigarettes containing the exemplified -alkyl-alpha pyrones are more coumarinlike and/or sweeter, warmer, spicier and more aromatic in nature than those cigarettes not containing these 6- alkyl-alpha pyrones whether or not ingredients of formulation A are included in the tobacco. I

It will be understood by those skilled in the art from the foregoing description that the -alkyl-alphapyrones of our invention can be used in the preparation of a wide variety of tobacco flavors and products.

EXAMPLE I1 TOBACCO FLAVOR FORMULATION CONTAINING 6-ALKYL-ALPHA-PYRONES A tobacco flavor formulation is prepared by admixing the following ingredients:

EXAMPLE III TOBACCO FLAVOR FORMULATION.

A tobacco flavoring formulation is prepared by admixing the following ingredients:-

Ingredients Parts Cinnamaldehyde 30.60 Nutmeg Oi1,'E1 0.50 Dibenzyl Ether .3.70 Eugenol I 1.20 4-methyl-6-n butyl-alpha-pyrone 3.00 Vanillin 0.50 3-Phenyl-4-pentenal dimethyl acetal 60.00

prepared according to the process disclosed in copending application for U.S. Letters Patent 276.922 filed on August 1, 1972 The foregoing formulation is added to smoking tobacco at the rate of 0.06-0.15% based on the dry weight of tobacco. The purpose of the use of the 3-phenyl-4- pentenal dimethyl acetal is to provide to the flavor on smoking a cinnamon powder aromaand taste. The 4- methyl-6-n-butyl-alpha-pyrone (concentration on tobacco: 1800-4500 ppm) acts as an excellent replacement for the coumarin, formerly used in this formulation, and also enables the previously-used quantity 'of Vanillin to be halved. I v

A formulation yielding substantially the same results is produced when one-half of the 4-me'thyl-6-n-butylalpha-pyroneused is replaced with an equal quantity (1.50 parts by weight) of 4-methyl-6-n-pentyl pyrone.

, EXAMPLE IV TOBACCO FLAVOR FORMULATION A tobacco flavoring formulation prepared by admixing the following ingredients:

The foregoing flavor is added to smoking tobacco at the rates of 0,10, 0.20 and0.30% based on the weight of dry tobacco. The tobacco isthen manufactured into cigarettes according to standard manufacturing practice. The purpose of the 3-phenyl-4-pentenal diethyl acetal is to cause the tobacco, on smoking, to have a hay-clover-like flavor with fruity notes. The 4-methyl- 6-n-pentyl-alpha-pyrone (at concentrations, based on the dry weight of tobacco, f 1200-36OO ppm) acts as Esters; an excellent replacement for the coumarin, previously Aldehydes; used in this formulation. Ketones;

What is claimed is: Acetals;

l. A process for altering the organoleptic properties Natural Oils and Extracts; of tobacco comprising the step of adding to tobacco a Lactones, tobacco flavoring composition comprising one or more E h 6-alkyl-alpha-pyrone compounds having the structure: pyrazines; and

Pyrroles 2. The process of claim 1 wherein the 6-alkyl-alphapyrone is 6-n-propyl-alpha-pyrone. 3. The process of claim 1 wherein the -alkyl-alphapyrone is -n-butyl-alpha-pyrone. l 5 4. The process of claim 1 wherein the 6-alkyl-alpha- 0 pyrone is 6-n-pentyl-alpha-pyrone. R 0

5. The process of claim 1 wherein the 6-alkyl-alphapyrone is 4-methyl-6-isopropyl-alpha-pyrone.

6. The process of claim 1 wherein the 6-alkyl-alphawherein R is selected from the group consisting of pyrone i 4 thyl-6-n-pentyl-alpha-pyrone. methyl and hydrogen, and R is C C alkyl and at least one tobacco flavoring additive selected from the group consisting of: 

1. A PROCESS FOR ALTERING THE ORGANOLEPTIC PROPERTIES OF TOBACCO COMPRISING THE STEP OF ADDING TO TOBACCO A TOBACCO FLAVORING COMPOSITION COMPRISING ONE OR MORE 6-ALKYL-ALPHAPYRONE COMPOUNDS, HAVING THE STRUCTURE:
 2. The process of claim 1 wherein the 6-alkyl-alpha-pyrone is 6-n-propyl-alpha-pyrone.
 3. The process of claim 1 wherein the 6-alkyl-alpha-pyrone is 6-n-butyl-alpha-pyrone.
 4. The process of claim 1 wherein the 6-alkyl-alpha-pyrone is 6-n-pentyl-alpha-pyrone.
 5. The process of claim 1 wherein the 6-alkyl-alpha-pyrone is 4-methyl-6-isopropyl-alpha-pyrone.
 6. The process of claim 1 wherein the 6-alkyl-alpha-pyrone is 4-methyl-6-n-pentyl-alpha-pyrone. 